Hydroformylation process and apparatus

Abstract

Disclosed are a method and an apparatus for hydroformylation. A hydroformylation synthesis reactor is provided, which comprises a lower spray self-suction reactor arranged at the top of the reactor, the lower spray self-suction reactor comprising a nozzle and fluidly connected suction section, mixing section and diffusion section in sequence, the nozzle being located in the suction section, and the suction section being in fluid communication with a raw material gas source; characterized in that the suction section is also in fluid communication with the portion above the liquid phase line of the reactor through a pipeline, and the reactor further comprises a gas distributor arranged in the reactor and in fluid communication with the raw material gas source.

Description

[0001] This invention patent application is a divisional application of the invention patent application with application number 201910550807.5, application date June 24, 2019, entitled "Hydroformylation Method and Apparatus". Technical Field

[0002] This invention relates to a hydroformylation synthesis method and apparatus, specifically to a method for preparing aldehydes from olefins and synthesis gases via hydroformylation, and the reaction apparatus and system used in this method. The method and reaction system of this invention can improve reaction efficiency, reduce equipment investment, and offer high economic benefits. Background Technology

[0003] The hydroformylation of olefins is an important organic synthesis reaction that plays a crucial role in modern industry. Its product, aldehydes, are very useful chemical intermediates that can be used to synthesize a variety of important chemical products. It is the largest-scale homogeneous catalytic reaction process to date. [Trzeciak, AM; Ziólkowski, JJ Coord. Chem. Rev. 1999, 190-192, 883-900.].

[0004] The main methods for producing aldehydes from olefin hydroformylation include low-pressure rhodium-catalyzed hydroformylation and high-pressure cobalt-catalyzed hydroformylation. Under certain conditions, the feed olefin and syngas (H2 / CO) are directly introduced into the catalyst solution in the reactor, where they react in the bulk liquid phase to produce aldehydes. In the olefin hydroformylation process using ligand-modified homogeneous catalysts, the inhomogeneity of concentration and temperature in the reaction solution significantly affects the reaction conversion rate, the space-time yield (STY, meaning the amount of olefin converted per unit time and per unit volume, based on the total reaction volume), and the positive-to-negative ratio of the products. Therefore, most units require stirring to enhance the gas-liquid contact and ensure thorough and homogeneous mixing of the materials. With increasing carbon chain length, the reactivity of olefin hydroformylation decreases, especially with the presence of internal olefins, where the decrease in reactivity is more pronounced, resulting in longer reaction residence times and more byproducts. Therefore, a reaction intensification method is needed to improve reaction efficiency and enhance the selectivity of the main reaction.

[0005] One modification method involves mixing the reaction solution using agitation. Reactors with impellers provide good mixing, but the agitator construction is complex, and in special cases, the agitator materials are expensive. Another disadvantage of using stirred reactors is that the agitator shaft must pass through the wall of the pressurized reactor, placing high demands on the equipment's sealing. Furthermore, the rotation of the agitator shaft puts significant stress on the reactor seal and the agitator impeller. During daily operation, stirring equipment is prone to failure, severely impacting the continuous and stable operation of production. Currently, most industrially applied olefin hydroformylation reactors use stirred tank reactors. Due to factors such as mass transfer, the reaction efficiency is relatively low. For example, in the industrial application of n-butene hydroformylation, a 70,000-ton / year 2-propylheptanol production unit requires three stirred reactors in series, each with a volume of approximately 105 m³. 3 (Mechanical Engineer, 2015(6): 252-254).

[0006] As an alternative to stirred tank reactors, bubble column reactors have been used in industry for the hydroformylation of olefins. The reactant gas is introduced from the bottom of the bubble column, and a gas distributor ensures that the reactant gas is dispersed in the reaction liquid to increase the mass transfer surface area. The bubbles rise dispersedly in the reaction liquid, thus mixing the reaction liquid. However, in a simple bubble column reactor, because the reactant gas participates in the hydroformylation reaction during its ascent, localized concentration gradients and temperature inhomogeneities are easily formed within the bubble column, thus affecting the reaction conversion rate, aldehyde selectivity, and space-time yield of aldehydes. The production efficiency is also lower than that of a stirred tank reactor.

[0007] CN 101679173B discloses a method and apparatus for preparing aldehydes by reacting olefins with a synthesis gas containing carbon monoxide and hydrogen. It employs an injector to enhance gas-liquid mass transfer, thereby improving the aldehyde conversion efficiency and obtaining a desirable high-yield aldehyde.

[0008] CN102272079A discloses an apparatus for preparing alcohols from olefins, comprising a hydroformylation reactor, the reactor including an injection device for injecting olefins and syngas into a catalyst mixture solution within the reactor, a reactor outlet for discharging the reaction mixture of the olefins and syngas, a distribution plate for altering the flow of the olefins and syngas, and a circulation pipe for recycling a portion of the reaction mixture to the injection device.

[0009] The article "Types and Applications of Jet Gas-Liquid Reactors" by Wang Xiaofu et al. (Chemical Industry and Engineering Technology, Vol. 23, No. 2, 2002) introduces jet gas-liquid reactors. It mentions that a typical industrially used type is the down-jet self-priming reactor, which consists of four parts: a nozzle, a suction chamber, a mixing chamber, and a diffusion chamber. When a reaction liquid with a certain pressure is injected downwards through the nozzle, a high flow velocity is generated, creating a pressure drop around the nozzle. This draws the side-supply raw material gas into the suction chamber, where it is thoroughly mixed to form turbulence, and the reaction occurs simultaneously. The product gradually decreases in velocity within the diffusion chamber, and the increased static pressure propels the product out. Because it can automatically draw in a large amount of gas without the need for compressors or other gas delivery equipment, energy consumption is greatly reduced. Furthermore, the stable turbulence formed at the nozzle enhances the mixing between the gas and liquid, which is highly advantageous for diffusion-controlled instantaneous gas-liquid phase reactions.

[0010] In the chemical industry, even a 1% increase in reaction efficiency can generate significant economic benefits. Although the introduction of jet-type gas-liquid reactors has improved the efficiency of olefin hydroformylation reactions, there is still room for further improvement in this method. Summary of the Invention

[0011] The purpose of this invention is to further improve the efficiency of olefin hydroformylation reaction.

[0012] Therefore, one aspect of the present invention relates to a hydroformylation synthesis reactor, which includes a down-spray self-priming reactor placed on top of the reactor, the down-spray self-priming reactor comprising, in sequence, a nozzle and a fluidly connected intake section, a mixing section and a diffusion section, the nozzle being located within the intake section and the intake section being in communication with a raw material gas source fluid;

[0013] The feature is that the gas intake section is also connected to the fluid above the liquidus line of the reactor through a pipe, and the reactor also includes a gas distributor inside the reactor and connected to the raw material gas source fluid.

[0014] Another aspect of the present invention relates to a reaction system for a hydroformylation synthesis reaction, comprising the hydroformylation synthesis reactor described in this invention, the reactor comprising:

[0015] The self-priming reactor installed on top of it includes, in sequence, a nozzle and a fluidly connected intake section, a mixing section and a diffusion section. The nozzle is located in the intake section, which is fluidly connected to the raw material gas source, and the intake section is also connected to the fluid above the liquidus line of the reactor through a pipe.

[0016] A gas distributor located inside the reactor and connected to the raw material gas source fluid;

[0017] The reactor outlet installed at its lower part is used to discharge the reaction mixture and catalyst solution; and

[0018] A distribution plate installed between the downspout self-priming reactor and the reactor outlet to alter the flow of the olefins and syngas;

[0019] The system also includes a circulation pipe for recovering the reaction mixture from the reactor outlet and then supplying it to the downspout self-priming reactor to circulate the reaction mixture and catalyst solution.

[0020] Another aspect of the present invention relates to a method for preparing aldehydes from olefins, comprising the following steps:

[0021] A hydroformylation synthesis reactor is provided, the top of which is equipped with a down-spray self-priming reactor. The down-spray self-priming reactor sequentially includes a nozzle and a fluidly connected intake section, a mixing section, and a diffusion section. The nozzle is located in the intake section, which is in communication with the raw material gas source fluid. The intake section is also in communication with the fluid above the liquidus line of the reactor through a pipe. The reactor also includes a gas distributor in communication with the raw material gas source fluid.

[0022] The catalyst-containing reaction liquid is injected into the reactor through the nozzle of the self-priming reactor. The reaction liquid entrains a portion of the gaseous raw material from the gas source and the circulating gas in the gas phase of the reactor in the gas intake section, and is mixed, reacted and diffused in the mixing section and the diffusion section.

[0023] Another portion of the gaseous raw material from the gas source is sent through a pipeline to the gas distributor inside the reactor, where it reacts with the catalyst-containing solution by bubbling in the reactor liquid.

[0024] Another aspect of the invention relates to the use of the aforementioned hydroformylation synthesis reactor in the preparation of aldehydes from olefins. Attached Figure Description

[0025] The invention is further illustrated below with reference to the accompanying drawings. In the drawings:

[0026] Figure 1 This is a schematic diagram of the structure of the downspout self-priming reactor used in this invention;

[0027] Figure 2 This is a simplified process flow diagram of an example of the present invention;

[0028] Figure 3 This is a simplified process flow diagram of another embodiment of the present invention;

[0029] Figure 4 This is a simplified process flow diagram of another embodiment of the present invention;

[0030] Figure 5 This is a simplified process flow diagram of a dual-injection reactor connected in series in one embodiment of the present invention;

[0031] Figure 6 This is a simplified process flow diagram of an example of the present invention, wherein the bottom-spray self-priming reactor is connected to the raw material gas source and the gas phase fluid of the reaction vessel through a Y-shaped air inlet pipe. Detailed Implementation

[0032] The inventors of this invention conducted a careful study of existing hydroformylation synthesis reactors and discovered that although the down-spray self-priming reactor has a force that pushes the reactants downwards, causing them to move into the bottom liquid catalyst solution, some reactants, especially the lighter synthesis gas, tend to remain suspended in the upper part of the reactor, such as at the top, thus affecting reaction efficiency. Based on this discovery, the inventors proposed introducing the gas from the gas phase of the reactor into the intake section of the down-spray self-priming reactor, circulating it back to the reactor for further reaction, thereby improving reaction efficiency.

[0033] Furthermore, the inventors of this invention have discovered that if a down-spray self-priming reactor is introduced into the bubbling tower reactor and gaseous raw materials are simultaneously introduced into the reactor through both the down-spray self-priming reactor and the gas distributor, the jetting force of the down-spray self-priming reactor will more or less act as agitation or stirring. This can advantageously utilize the advantages of the bubbling tower reactor while eliminating defects such as localized concentration gradients and temperature inhomogeneities present in conventional bubbling tower reactors.

[0034] Therefore, this invention relates to a hydroformylation synthesis reactor. The shape, material, and size of the reactor itself are not particularly limited, and it can be a conventional reactor known in the art. In one embodiment of this invention, the reactor is a vertical reactor. In another embodiment of this invention, the reactor is a horizontal reactor.

[0035] The reaction vessel of the present invention includes a bottom-spray self-priming reactor placed on top of the reaction vessel. The bottom-spray self-priming reactor includes, in sequence, a nozzle and a fluidly connected intake section, a mixing section and a diffusion section. The nozzle is located in the intake section and the intake section is in communication with the raw material gas source fluid. The intake section is also in communication with the part above the liquidus line or the gas phase part of the reaction vessel through a pipe.

[0036] In this invention, the term "the nozzle is located within the intake section" is not limited to the nozzle being physically located within the intake section. The nozzle can maintain various positional relationships with the intake section, as long as the sprayed material can entrain gaseous raw materials and gases originating from the gas phase portion of the reactor while being injected into the intake section. For example, the nozzle can be located at the edge of the intake section, with a spray pressure sufficient to entrain gaseous raw materials.

[0037] In this invention, the term "pipeline" in the phrase "the intake section is also fluidly connected to the portion above the liquidus line or the gas phase portion of the reactor via a pipeline" refers to any pipeline other than the main body pipeline of a conventional downspray self-priming reactor. This pipeline is located outside the reactor.

[0038] In this invention, the term "above the liquidus line of the reactor" refers to the location of the reactor above the liquidus line and where no liquid is drawn in during the gas-phase circulation. In one embodiment of the invention, the portion above the liquidus line refers to the location near and including the top of the reactor. In another embodiment of the invention, the portion above the liquidus line refers to the top of the reactor.

[0039] In this invention, the term "downspray self-priming reactor comprising a fluidly connected intake section, mixing section and diffusion section" means that the reactor comprises three functional sections with intake, mixing and diffusion functions. The functional sections may be physically distinguishable (e.g., intake chamber, mixing chamber and diffusion chamber) or physically indistinguishable (e.g., a section of pipe, each of which has intake, mixing or diffusion functions at different locations).

[0040] In this invention, the terms "fluid interconnected" and "fluid connected" are used interchangeably, referring to two parts that are connected to each other and fluid can flow between the two parts.

[0041] In one embodiment of the present invention, the gas intake section has two gas inlets, one of which is fluidly connected to the raw material gas source, and the other is fluidly connected to the part above the liquidus line of the reactor, preferably the top of the reactor, through a pipe.

[0042] In one embodiment of the present invention, the intake section has a gas inlet, which is connected to the raw material gas source and the fluid above the liquidus line of the reactor via a Y-shaped pipe.

[0043] In one embodiment of the invention, the intake section has two gas inlets, one of which is fluidly connected to a raw material gas source, and the other is fluidly connected via a pipe to the portion of the reactor above the liquidus line. In one embodiment, the height of the nozzle orifice is lower than at least one of the gas inlets, and preferably lower than both of the gas inlets simultaneously.

[0044] In one embodiment of the present invention, the intake section has two gas inlets of equal height, one of which is fluidly connected to the raw material gas source, and the other is fluidly connected to the portion above the liquidus line of the reactor via a pipe, with the nozzle orifice at a height lower than the gas inlet.

[0045] In one embodiment of the invention, the intake section has two gas inlets, one of which is fluidly connected to the raw material gas source, and the other is fluidly connected to the portion of the reactor above the liquidus line via a pipe. The nozzle orifice is 0.5-500 mm lower than the lowest point of at least one of the gas inlets, preferably 10-350 mm lower, more preferably 20-250 mm lower, and most preferably 50-200 mm lower. In another embodiment of the invention, the nozzle orifice is 0.5-30 mm lower than the lowest point of at least one of the gas inlets, preferably 0.8-20 mm lower, and more preferably 1-10 mm lower. Preferably, it is 1.1-5 mm lower.

[0046] In one embodiment of the invention, the height difference between the two gas inlets is less than 100 mm. Preferably less than 50 mm, more preferably less than 10 mm, more commonly less than 5 mm, and most preferably less than 1 mm.

[0047] The structure of the down-spray self-priming reactor of the present invention is not particularly limited and can be a conventional structure known in the art. For example, the down-spray self-priming reactor described in "Types and Applications of Jet Gas-Liquid Reactors" by Wang Xiaofu et al. (Chemical Industry and Engineering Technology, Vol. 23, No. 2, 2002) is an example, except that the gas inlet section has two gas inlets or the gas inlet of the gas inlet chamber is connected to the two gas streams through a Y-shaped pipe.

[0048] In one example of the present invention, Chinese patent CN102272079A is used. Figure 1 The disclosed down-spray reactor, except that the gas inlet of the gas inlet section has two gas inlets or the gas inlet of the gas inlet of the gas inlet chamber is connected to two gas streams through a Y-shaped pipe.

[0049] Figure 1 This is a schematic diagram of the structure of a bottom-spray self-priming reactor according to an example of the present invention. As shown in the figure, the bottom-spray self-priming reactor of the present invention includes, in sequence, a nozzle 1, a suction chamber 2, a mixing chamber 3, and a diffusion chamber 4. The nozzle 1 is located inside the suction chamber 2. The suction chamber 2 has a gas inlet 6 that is fluidly connected to a gas source and a gas inlet 7 that is fluidly connected to the part above the liquidus line of the reactor (preferably the top of the reactor).

[0050] During operation, the catalyst-containing liquid stream 5 is sprayed downward through nozzle 1. The pressure of the spray entrains the raw material gas introduced through raw material gas inlet 6 and the gas from the gas phase of the reactor introduced through circulating gas inlet 7. The three are fully mixed and reacted in the movement path from the suction chamber 2 to the mixing chamber 3, and then diffused into the reactor through the diffusion chamber 4.

[0051] In one embodiment of the invention, the gas chamber 2, mixing chamber 3, and diffusion chamber 4 constitute a Venturi tube. For example... Figure 1As shown. The inlet section of the intake chamber 2 is connected to the nozzle 1. The lower part of the intake chamber is a conical tube constriction section. The mixing chamber 3 forms the throat of the venturi tube, and the diffusion chamber 4 forms the diffusion section of the venturi tube.

[0052] In one embodiment of the invention, the diameter D of the inlet section of the suction chamber 2 connected to the nozzle 1 is 0.8-500 mm, preferably 1-400 mm, more preferably 1.5-300 mm, and most preferably 1.75-250 mm, with a preferred diameter of 2-100 mm; the cone angle of the nozzle conical tube is approximately 10-90 degrees, preferably 15-75 degrees, and more preferably 20-60 degrees. The diameter of the throat is 1.0-3.0D, and its length is 5-100 times the throat diameter, preferably 20-60 times. The cone angle of the diffuser section is approximately 5-30 degrees, preferably 9-20 degrees, and more preferably 10-15 degrees; the diameter at the outlet of the diffuser section is approximately 1.0-20 times the throat diameter, preferably 1.2-18 times, more preferably 1.5-15 times, and most preferably 2-10 times.

[0053] In one embodiment of the present invention, the total length of the venturi tube is 0.01-1.5 times the internal height of the reactor, preferably 0.05-1.4 times, more preferably 0.08-1.2 times, more preferably 0.1-1.1 times, more preferably 0.2-1 times, and most preferably 0.2-0.95 times.

[0054] The reaction vessel of the present invention includes a gas distributor connected to the raw material gas fluid inside the reaction vessel for bubbling in the reaction liquid containing the catalyst, so that the unreacted material in the downspray self-priming reactor can continue to react in the reaction vessel liquid, thereby further improving the reaction efficiency.

[0055] In a preferred embodiment of the present invention, the amount of raw material gas input to the gas distributor accounts for 30%-95% of the total amount of raw material gas, preferably 40%-90%, more preferably 50%-85%, and most preferably 60%-85%.

[0056] There are no particular restrictions on the location of the gas distributor within the reactor, as long as it can bubble in the reaction liquid containing the catalyst. After reading this disclosure, those skilled in the art can easily determine a suitable location for the gas distributor.

[0057] There are no particular limitations on the gas distributor used in the reactor of this invention; it can be any gas distributor known in the art. After reading the disclosure of this invention, those skilled in the art can easily determine a suitable gas distributor and its installation dimensions. For example, those skilled in the art can select a suitable gas distributor based on the article "Design of Gas Distributor in Bubble Bed and Its Influence on Hydraulics" by Zhang Kai et al. (Coal Chemical Industry, February 1995).

[0058] In one embodiment of the present invention, 100% of the olefins enter the gas distributor, and the unreacted feed gas is entrained into the injector through the gas phase of the reactor, where it is further reacted under the action of a catalyst.

[0059] In one embodiment of the present invention, the olefins of the hydroformylation synthesis reaction of the present invention are injected together with the catalyst solution into the gas intake section through a nozzle. At the same time as injection, the raw material gas and the gas phase of the reaction vessel are entrained, and the three are mixed and reacted to form the desired reaction product.

[0060] In one embodiment of the invention, the olefin used in the hydroformylation synthesis reaction of the invention is a gaseous olefin. In this case, the catalyst-containing liquid stream 5 includes a fresh catalyst solution and / or a recycled catalyst solution and optionally a feedstock olefin. The feedstock gas drawn in through the feedstock gas inlet 6 includes syngas and optionally a feedstock olefin. The gas drawn in through the recycled gas inlet 7 is a gas originating from the gas phase portion of the reactor. The gas flow introduced into the gas distributor includes syngas and / or gaseous olefin.

[0061] In another embodiment of the invention, the olefin used in the hydroformylation synthesis reaction described herein is a liquid olefin. In this case, the liquid stream 5 includes the olefin, a fresh catalyst solution and / or a recycled catalyst solution. The feed gas drawn in through the feed gas inlet 6 includes synthesis gas. The gas drawn in through the recycled gas inlet 7 is gas originating from the gas phase portion of the reactor. The gas flow introduced into the gas distributor includes synthesis gas.

[0062] In this invention, the synthesis gas is a CO / H2 mixture, which can be easily produced by conventional methods, such as conventional water gas synthesis.

[0063] The present invention also relates to a reaction system for a hydroformylation synthesis reaction, comprising the hydroformylation synthesis reactor of the present invention, the reactor comprising a self-priming reactor of the present invention mounted on its top for injecting feedstock olefins, synthesis gas (CO / H2), catalyst solution, and reactor gas phase recirculation feed into the reactor; a reactor outlet mounted on its lower part for discharging the reaction mixture and catalyst solution; a distribution plate mounted between the self-priming reactor and the reactor outlet for altering the flow of the olefins and synthesis gas; a circulation pipe for recovering the reaction mixture and catalyst solution from the reactor outlet and then supplying it to the self-priming reactor to circulate the reaction mixture; and a gas distributor mounted below the liquidus line of the reactor and fluidly connected to the feedstock gas source for generating bubbles.

[0064] In this invention, the term "lower part of the reactor" refers to the location below the liquidus line of the reactor. In one embodiment of the invention, the "lower part of the reactor" includes the bottom of the reactor.

[0065] A distribution plate installed inside the reactor is used to alter the flow of the jet stream in a self-priming reactor, thereby adjusting the residence time of the reactants in the reactor. Those skilled in the art can easily determine the position and shape of the distribution plate in the reactor according to specific reaction requirements. For example, those skilled in the art can determine the position and shape of the distribution plate in the reactor based on the specific reaction and the distribution plate shape and installation requirements disclosed in Chinese Patent CN102272079A.

[0066] Figure 2 This is a schematic diagram of the reaction process of an example of the present invention. Figure 2 As shown, the reaction system for hydroformylation synthesis of the present invention includes the hydroformylation synthesis reactor 10 of the present invention. The reactor 10 includes a bottom-spray self-priming reactor 16. The gas intake section of the reactor 16 has two independent gas inlets, one of which is fluidly connected to the gas phase part of the reactor, and the other is fluidly connected to the raw material gas source. Reactor 16 is installed at the top of the reactor vessel and is used to inject the feed olefins, syngas (CO / H2), and fresh catalyst solution (if necessary) fed through pipes 110 and 111B, the reactor gas phase recirculation feed circulated through pipe 19, and the catalyst-containing solution circulated through pipes 113 and 114 into the reactor vessel through nozzle 17 for simultaneous reaction; a reactor outlet is installed at the bottom of the reactor vessel and connected to pipe 112 for discharging the reaction mixture containing the catalyst solution; a distribution plate 12 is installed between the down-spray self-priming reactor 16 and the reactor outlet for changing the flow of the olefins and syngas; and a circulation pipe 114 is used to recover the reaction mixture from the reactor outlet through pipe 113 and then supply it to the down-spray self-priming reactor 16 through nozzle 17 to circulate the reaction mixture.

[0067] In one embodiment of the invention, the reaction system further includes a vacuum flash tank 22 fluidly connected to the outlet of the reactor, and an aldehyde evaporator 23 fluidly connected to the vacuum flash tank 22. The bottom of the aldehyde evaporator 23 is fluidly connected to the nozzle 17 of the bottom spray self-priming reactor 16 of the reactor via pipes 124, 125, 113 and 114.

[0068] In operation, when the olefin feedstock is in a liquid state, the nozzle 17 of the down-spray self-priming reactor 16 sprays the liquid olefin solution and fresh catalyst solution (if necessary) input through pipe 110, the catalyst-containing solution circulating from the reactor through pipe 112, and the catalyst-containing recovered liquid circulating from the aldehyde evaporator 23 through pipe 125 into the reactor 10. Simultaneously, it entrains the synthesis gas (CO / H2) input through pipe 111B and the gas phase portion of the reactor gas transported through pipe 19. The sprayed material is mixed, reacted, and diffused in the diffusion section 18, and after being blocked by the baffle 12, it is further distributed and reacted in the reactor. Another stream of synthesis gas 111A is directly input into the gas distributor 11 below the liquidus line in the reactor without depressurization, bubbling the reaction liquid to allow the unreacted olefins to react further under the action of the catalyst. The reaction mixture is transported through pipes 113 and 114 from the lower (preferably bottom) outlet of the reactor by the action of the jet circulation pump 13. Part of it is sent to the nozzle 17 through pipe 114 after heat exchange by the circulating liquid heat exchanger 14, and the other part is sent to the vacuum flash tank 22 through pipe 120. The tail gas of the vacuum flash tank 22 is vented through pipe 121. The flash product enters the aldehyde evaporator 23 through pipe 122. The final aldehyde product is recovered through pipe 123. The distillation residue (a solution containing the catalyst) is transported to the nozzle 17 for recycling by the action of the circulation pump 24 through pipes 124 and 125.

[0069] When the olefin feedstock is in a gaseous state, the nozzle 17 of the down-spray self-priming reactor 16 injects fresh catalyst solution (if necessary) and optional feedstock olefins, a catalyst-containing solution from the reactor circulated via pipe 112, and a catalyst-containing recovered liquid from the aldehyde evaporator 23 circulated via pipe 125 into the reactor 10. Simultaneously, it entrains syngas (CO / H2) input via pipe 111B, optional gaseous olefins, and a portion of the gas phase from the reactor transported via pipe 19. The injected material is mixed, reacted, and diffused in the diffusion section 18, and further distributed and reacted in the reactor after being blocked by baffle 12. Another stream of unrepressurized syngas 111A and / or gaseous olefins is directly input into the gas distributor 11 below the liquidus line in the reactor to bubble the reaction liquid, allowing unreacted olefins to react further under the action of the catalyst. The reaction mixture is transported through pipes 113 and 114 from the lower (preferably bottom) outlet of the reactor by the action of the jet circulation pump 13. Part of it is sent to the nozzle 17 through pipe 114 after heat exchange by the circulating liquid heat exchanger 14, and the other part is sent to the vacuum flash tank 22 through pipe 120. The tail gas of the vacuum flash tank 22 is vented through pipe 121. The flash product enters the aldehyde evaporator 23 through pipe 122. The final aldehyde product is recovered through pipe 123. The distillation residue (a solution containing the catalyst) is transported to the nozzle 17 through pipe 124 for recycling by the action of the circulation pump 24.

[0070] In one embodiment of the present invention, the reaction system comprises 1-2 hydroformylation synthesis reactors 10, each reactor comprising 1-2 down-spray self-priming reactors 16, and each equipped with a gas phase circulation line 19 and liquid phase circulation lines 113, 114, and 125. The nozzles 17 of the down-spray self-priming reactors 16 inject a catalyst-containing reaction liquid, raw material olefins, synthesis gas, and a mixture of unreacted raw materials from the top of the reactor into the reactor. Most of the hydroformylation of the raw material olefins is completed within the down-spray self-priming reactors 16. The remaining unreduced synthesis gas and / or olefins (when the olefins are gaseous) are transported to a gas distribution gas below the liquidus line of the reactor, where bubbling occurs in the liquid phase, thereby further carrying out the hydroformylation of the raw material olefins within the reactor outside the down-spray self-priming reactor. Each reactor is equipped with an independent heat exchanger for heat transfer or heating, installed on the circulation line.

[0071] In one embodiment of the present invention, the catalyst used comprises a Group VIII metal element and a phosphorus-containing ligand.

[0072] In one embodiment of the present invention, the reaction system includes at least one evaporator to perform catalyst recycling and separation of aldehyde products.

[0073] In one embodiment of the present invention, the raw material olefin is selected from ethylene, propylene, 1-butene, 2-butene, isobutene, pentene, 2,5-dihydrofuran, C6-C 18 At least one of the alkene compounds.

[0074] In one embodiment of the invention, the ratio of the volumetric flow rate of the circulating injection liquid per hour to the effective loading volume of the reactor is 10-60, preferably 20-40.

[0075] In one embodiment of the present invention, a gas phase circulation is formed between the reaction vessel and the down-spray self-priming reactor via pipe 19, wherein the ratio of the self-circulating gas volume flow rate to the circulating spray liquid volume flow rate is 0.5-4; preferably 1-2.

[0076] In one embodiment of the present invention, each reactor is equipped with one or two down-spray self-priming reactors and one or two heat exchange devices for heat transfer or heating of the reaction system. The heat exchange devices are installed on the circulation pipe and are located between the down-spray self-priming reactor 16 and the jet circulation pump 13.

[0077] In one embodiment of the present invention, the catalyst composition selected is an acetylacetone carbonyl rhodium compound precursor, and the selected phosphorus ligand is a composition of tris(o-methylphenyl)phosphine and a bisphosphite; the selected phosphorus ligand is a composition of tris(o-methylphenyl)phosphine and a monophosphite; wherein the structure of the bisphosphite is as follows:

[0078]

[0079] The structure of the monophosphonate is as follows:

[0080]

[0081] In one embodiment of the present invention, the catalyst composition selected is a triphenylphosphine acetylacetone carbonyl rhodium compound precursor, and the phosphorus ligand selected is triphenylphosphine.

[0082] In one embodiment of the present invention, the evaporator can be a shell-and-tube heat exchanger, a falling film evaporator, etc., to achieve catalyst reuse and aldehyde product separation. When the product aldehyde has a high boiling point, the catalyst and aldehyde product can be separated by depressurization.

[0083] In one embodiment of the invention, when the reaction system comprises two or more hydroformylation reactors, the reactors are connected in series.

[0084] Figure 3 This is a schematic diagram of a reaction system according to an example of the present invention. The reaction vessel 100 of this system includes two parallel-arranged down-spray self-priming reactors. Figure 3 As shown, in one embodiment of the invention, the reaction mixture output from the lower part of the reactor 100 via pipe 113 is divided into two streams, which are heat-exchanged by circulating pumps 102A and 102B and circulating liquid heat exchangers 103A and 103B, respectively, to form circulating liquids 115A and 115B. Circulating liquid 115A is mixed with raw material olefin 111A (e.g., when the raw material olefin is liquid) and circulating catalyst 120A and then enters the nozzle of a down-spray self-priming reactor 105, entraining the first stream of syngas 110 and the gaseous components from the top of the reactor conveyed via pipe during injection. Circulating liquid 115B is mixed with raw material olefin 111B (e.g., when the raw material olefin is liquid) and circulating catalyst 120B and then enters the nozzle of another parallel down-spray self-priming reactor, entraining the syngas 110 and the gaseous components from the top of the reactor conveyed via pipe 107 during injection. The second stream of syngas 110A (not shown in the figure) is directly fed into the gas distributor 11 inside the reactor 100, where it undergoes a catalytic reaction with the unreacted olefins in the reactor liquid while being bubbled.

[0085] When the raw material olefin is in a gaseous state, a portion of the olefin in the above reaction system is entrained and added together with the synthesis gas 110 instead of having to be injected through the nozzle, while another portion of the synthesis gas 110A is sent to the gas distributor together with the optional olefin for bubbling reaction.

[0086] In operation, the reaction mixture output from the lower part of reactor 100 via pipe 113 is divided into two streams, which are then heat-exchanged by circulating pumps 102A and 102B, pipes 114A and 114B, and circulating liquid heat exchangers 103A and 103B, respectively, forming circulating liquids 115A and 115B. A portion of the reaction mixture is sent to a vacuum flash evaporator 108 via pipe 116, and the exhaust gas from the vacuum flash evaporator 108 is vented via pipe 118. The flash evaporation product enters an aldehyde evaporator 109 via pipe 117, and the final aldehyde product is recovered via pipe 119. The distillation residue (a solution containing the catalyst) is transported back to the reactor via pipe 120 for recycling.

[0087] Figure 4 This is a schematic diagram of an example of the present invention, in which the reaction vessel 100 of the reaction system comprises two parallel-arranged down-spray self-priming reactors. For example... Figure 4 As shown, the circulating liquid 113 output from the lower part of the reactor 100 passes through the circulating pump 102 and the circulating heat exchanger 103, and is mixed with the feed olefin 111 (when the feed olefin is in a liquid state), an optional fresh catalyst solution, and the circulating catalyst 120. It is then divided into two streams, which enter the nozzles of two parallel down-spray self-priming reactors 104 and 105, respectively. Each down-spray self-priming reactor independently entrains the feed synthesis gas (optionally including the feed olefin when it is in a gaseous state) and entrains the gas phase from the top of the reactor through the gas phase circulation line 107. In the mixing section of the down-spray self-priming reactor, the gas and liquid phases come into full contact, forming microbubbles, which then enter the diffusion section of the down-spray self-priming reactor. Most of the reaction is completed within the down-spray self-priming reactor. Similarly, a portion of the synthesis gas and optional olefins are fed into the gas distributor 11 inside the reactor for bubbling reaction.

[0088] Figure 5 This is a schematic diagram of a reaction system according to another embodiment of the present invention. Figure 5As shown, the reaction system includes two reactors 100A and 100B arranged in series, with their gaseous portions fluidly connected via pipe 114. In operation, the reaction mixture output from the lower part of the first reactor 100A is divided into two streams via pipe 112A and a circulating pump 102A. One stream passes through a circulating heat exchanger 103A, mixes with the raw material 111 (e.g., when the olefin is liquid), and a circulating catalyst 122, and then enters the nozzle 105A of the self-priming reactor 104A in reactor 100A. The other stream circulates back to reactor 100B. Reactor 100A is equipped with a gas distributor 11 fluidly connected to the raw material gas source. A portion of the synthesis gas and, optionally, the olefin are fed into this gas distributor for bubbling reaction. In reactor 100B, the reaction mixture output from the lower outlet of reactor 100B via pipe 112B is divided into two streams via circulating pump 102B. One stream, after passing through the circulating heat exchanger 103B, is fed into the nozzle 105B of the self-priming downspout reactor 104B via pipeline 115B. When sprayed into the reactor 100B, the nozzle 105B entrains the syngas 110B and the gaseous components from the reactor transported via pipeline 107B. The other stream is transported via pipeline 116 to the vacuum flash evaporator 108, where it undergoes flash separation and then enters the aldehyde evaporator 109 via pipeline 117 for further separation and recovery. A gas distributor 11 can be optionally installed in the reactor 110B, allowing some raw materials to be directly fed to this gas distributor for bubbling reaction.

[0089] Figure 6 This is a schematic diagram of the reaction process of an embodiment of the present invention. Figure 2 In contrast, reactor 16 has only one gas inlet in its intake section, which is connected to both the gas source and the fluid at the top of the reactor via a Y-shaped pipe. The remaining structural functions are the same. Figure 2 same.

[0090] This invention also relates to a method for preparing aldehydes from olefins, comprising the following steps:

[0091] A hydroformylation synthesis reactor is provided, the top of which is equipped with a down-spray self-priming reactor. The down-spray self-priming reactor sequentially includes a nozzle, a gas intake section connected to the fluid, a mixing section, and a diffusion section. The nozzle is located in the gas intake section, which is in communication with the raw material gas source fluid. The gas intake section is also connected to the part of the reactor above the liquidus line through a pipe. The reactor also includes a gas distributor inside the reactor and connected to the raw material gas source fluid.

[0092] A catalyst-containing solution is injected into the reactor via the nozzle of the self-priming down-spray reactor. The solution entrains a portion of the raw material gas from the gas source and components of the gas phase portion of the reactor in the gas intake section, and mixes, reacts and diffuses in the mixing section and the diffusion section.

[0093] Another portion of the raw material gas is fed into the gas distributor inside the reactor, causing it to bubble in the reactor liquid and further undergo a hydroformylation reaction under the action of a catalyst.

[0094] In the method of this invention, the conditions for the hydroformylation reaction are not particularly limited and can be reaction conditions known in the art. In one example of this invention, the hydroformylation reaction conditions described in Chinese Patent CN102272079A are used, which is incorporated herein by reference as a part of this invention.

[0095] In one embodiment of the present invention, the raw material olefin is in liquid state. The down-spray self-priming reactor is located at the top of the reactor. The catalyst-containing circulating liquid from the reactor, the raw material olefin, and the circulating catalyst liquid from the aldehyde evaporator are mixed and then entrained in the raw material syngas and the mixed gas phase at the top of the reactor in the down-spray self-priming reactor. The gas and liquid are in full contact and are sprayed into the reaction liquid through the diffusion section. At the same time, a portion of the syngas is sent to the gas distributor, where it bubbles in the reactor liquid and reacts further with the remaining olefin under the action of the catalyst.

[0096] In one embodiment of the present invention, the raw material olefin is in a gaseous state. The down-spray self-priming reactor is located at the top of the reactor. The catalyst-containing circulating liquid from the reactor, the circulating catalyst liquid from the aldehyde evaporator, and the optional olefin are mixed and then entrained in the down-spray self-priming reactor. The gas and liquid are in full contact and are sprayed into the reaction liquid through the diffusion section. At the same time, a portion of the syngas and an optional portion of the olefin are sent to the gas distributor, where they bubble in the reactor liquid and react further with the remaining olefin under the action of the catalyst.

[0097] This invention utilizes liquid-phase entrainment of the gas phase to create a gas-phase circulation between the gas phase space of the reactor and the down-spray self-priming reactor. Within the spray reactor, the raw material syngas, the gas phase components of the reactor, the catalyst solution, and the olefin feedstock are in full contact. Experiments have shown that the reaction rate is accelerated due to the ample contact between a large amount of hydrogen and the reaction liquid containing the catalyst composition. Simultaneously, by adding a portion of the syngas via bubbling while using the down-spray self-priming reactor, the syngas flow rate is reduced compared to conventional simple bubbling tower reactors, which helps mitigate the adverse effects of uneven concentration and temperature gradients. Furthermore, the spray from the down-spray self-priming reactor provides some degree of stirring, helping to eliminate the adverse effects of uneven temperature gradients.

[0098] Furthermore, unexpected experimental results were obtained, where the conversion rate of olefins (e.g., propylene) relative to the feed olefins can reach over 70% within the confined space of the jet reactor. Unreacted olefins undergo a bubbling reaction within the reactor via injection, further enhancing the olefin conversion rate. Due to the intensified reaction, extremely high olefin conversion rates can be achieved using a jet reactor equipped with gas-phase and liquid-phase circulation loops and a gas distributor, eliminating the need for subsequent olefin stripping separation processes. The increased reaction efficiency allows for a reduction in the volume and number of reactors, shortens the reaction residence time, further improves the selectivity of the aldehyde product, and reduces the initial catalyst input. Compared to bubbling reactors, this invention eliminates the adverse effects of uneven concentration and temperature gradients. Compared to traditional stirred tank reactors, the liquid phase formed within the injection pipe has a higher syngas concentration, resulting in better gas-liquid mixing, faster reaction speeds, a simple and reliable nozzle structure, low investment costs, and the elimination of instability factors associated with mechanical stirring.

[0099] This invention primarily addresses the technical problems of existing reactors, such as large volume, numerous reactors, high power consumption, low reaction efficiency, and complex reaction processes. The invention designs a combined bubbling and jetting reactor device. By utilizing the high pressure of the syngas source, a gas distributor directly introduces the gas into the reactor liquid, creating a superior bubbling effect. Simultaneously, a combination of a gas-phase self-circulation loop and a liquid-phase jetting circulation further enhances gas-liquid mass transfer, significantly improving reaction efficiency. The bubbling bed completes part of the hydroformylation reaction of the raw material olefins, while the incompletely converted olefins undergo further hydroformylation in a smaller jetting device, effectively increasing the olefin conversion rate and reducing the unit consumption of the jetting circulation pump.

[0100] In one embodiment of the present invention, under conditions of 60-130°C and a reaction pressure of 1.0-6.0 MPa, an aldehyde is used as a solvent, and a catalyst formed by a Group VIII metal element and a phosphorus-containing ligand catalyzes the hydroformylation of an olefin to synthesize an aldehyde. The olefin is at least one selected from propylene, ethylene, butene, pentene, hexene, heptenene, and olefins with 6 to 18 carbon atoms. The olefin conversion rate can reach over 99%, achieving intensification of the olefin hydroformylation reaction process. This technical solution effectively solves the aforementioned problems and can be used in the process of producing aldehydes from olefin hydroformylation. Furthermore, it reduces the initial catalyst input cost and correspondingly reduces ligand consumption.

[0101] Example

[0102] The present invention will be further illustrated below through examples.

[0103] Example 1

[0104] use Figure 2The reaction system shown was tested using propylene as the olefin feedstock. The catalyst concentration was 80 ppm rhodium, and the ligands were a combination of tris(o-methylphenyl)phosphine L0 and L4, with a molar ratio of Rh:L0:L4 of 1:10:4. The reactor temperature was maintained at 90°C, the reaction pressure at 1.6 MPa, the effective reaction liquid volume of reactor 10 was 10 L, the reactor height was 900 mm, and a self-priming injector 16 was installed at the top. The injector had a nozzle diameter of 2.5 mm, a spray angle of 30°, a spray expansion tube diameter of 20 mm, and a spray tube expansion tube length of 850 mm. The injector 16 had two gas inlets in its intake section, connected to a gas source and a fluid source at the top of the reactor, respectively.

[0105] An ejector 16 is installed at the top of the reactor. The circulating liquid 112 is taken from the bottom of the reactor, mixed with the circulating catalyst solution 125, and then mixed with the propylene feed 110 after passing through the circulating pump 13 and the circulating heat exchanger 14. It then enters the ejector 16. In addition to entraining the feed synthesis gas 111B, the liquid phase also entrains a large amount of the mixed gas phase consisting of unreacted propylene, synthesis gas, and some products at the top of the reactor through the gas circulation pipe 19. This forms a full contact between the gas and liquid phases inside the nozzle. The liquid phase carries a large number of tiny bubbles into the diffuser section of the ejector.

[0106] Syngas feed 111A is fed into gas distributor 11 without depressurization, where it undergoes a bubbling reaction in the liquid phase containing the catalyst and reaction mixture. The reaction product 120 is then passed through a vacuum flash evaporator 22, where the liquid product (aldehyde removal) is separated from the catalyst in an evaporator, and the recycled catalyst 125 is returned to reactor 10.

[0107] In this embodiment, synthesis gas 111A has a flow rate of 1540 NL / h and a feed pressure of 5.5 MPa, which is reduced to 1.6 MPa through a gas distribution pipe; 111B has a flow rate of 380 NL / h and a feed pressure of 2.0 MPa; propylene feed 110 has a flow rate of 1.8 kg / h; the circulating liquid volumetric flow rate is 150 L / h; and the gas circulation rate is 170 L / h. The butyraldehyde yield is 3.06 kg / h, which translates to a propylene-to-butyraldehyde conversion rate of 99.1%. The measured space-time yield of butyraldehyde is STY = 4.25 mol / (l*h), and the product normal-to-isopropanoid ratio is 35. Due to the intensified reaction and low catalyst concentration, only one evaporator is needed to separate the catalyst and the product aldehyde, and the product aldehyde contains virtually no olefins.

[0108] Example 2

[0109] use Figure 2The reaction system shown was tested using propylene as the olefin feedstock. The catalyst had a rhodium concentration of 80 ppm, and the ligands were a combination of tris(o-methylphenyl)phosphine L0 and L5, with a molar ratio of Rh:L0:L5 of 1:10:4. The reactor temperature was maintained at 90°C, the reaction pressure at 1.6 MPa, the effective reaction liquid volume of reactor 10 was 10 L, the reactor height was 900 mm, and a self-priming injector 16 was installed at the top. The injector had a nozzle diameter of 2.5 mm, a spray angle of 30°, a spray expansion tube diameter of 20 mm, and a spray tube expansion tube length of 850 mm. The injector 16 had two gas inlets in its intake section, connected to a gas source and a fluid source at the top of the reactor, respectively.

[0110] An ejector 16 is installed at the top of the reactor. The circulating liquid 112 is taken from the bottom of the reactor, mixed with the circulating catalyst solution 125, and then mixed with the propylene feed 110 after passing through the circulating pump 13 and the circulating heat exchanger 14. It then enters the ejector 16. In addition to entraining the feed synthesis gas 111B, the liquid phase also entrains a large amount of the mixed gas phase consisting of unreacted propylene, synthesis gas, and some products at the top of the reactor through the gas circulation pipe 19. This forms a full contact between the gas and liquid phases inside the nozzle. The liquid phase carries a large number of tiny bubbles into the diffuser section of the ejector.

[0111] Syngas feed 111A is fed into gas distributor 11 without depressurization, where it undergoes a bubbling reaction in the liquid phase containing the catalyst and reaction mixture. The reaction product 120 is then passed through a vacuum flash evaporator 22, where the liquid product (aldehyde removal) is separated from the catalyst in an evaporator, and the recycled catalyst 125 is returned to reactor 10.

[0112] In this embodiment, synthesis gas 111A has a flow rate of 1540 NL / h and a feed pressure of 5.5 MPa, which is reduced to 1.6 MPa through a gas distribution pipe; 111B has a flow rate of 380 NL / h and a feed pressure of 2.0 MPa; propylene feed 110 has a flow rate of 1.8 kg / h; the circulating liquid volumetric flow rate is 150 L / h; and the gas circulation rate is 170 L / h. The butyraldehyde yield is 3.06 kg / h, which translates to a propylene-to-butyraldehyde conversion rate of 99.2%. The measured butyraldehyde space-time yield (STY) is 4.25 mol / (l*h), and the product normal-to-isotropic ratio is 32.

[0113] Example 3

[0114] use Figure 2The reaction system shown was tested using propylene as the olefin feedstock. The catalyst concentration was 80 ppm rhodium, and the ligands were a combination of tris(o-methylphenyl)phosphine L0 and monophosphite L7, with a molar ratio of Rh:L0:L7 of 1:10:4. The reactor temperature was maintained at 90°C, the reaction pressure at 1.6 MPa, the effective reaction liquid volume of reactor 10 was 10 L, the reactor height was 900 mm, and a self-priming injector 16 was installed at the top. The injector had a nozzle diameter of 2.5 mm, a spray angle of 30°, a spray expansion tube diameter of 20 mm, and a spray tube expansion tube length of 850 mm. The injector 16 had two gas inlets in its intake section, connected to a gas source and a fluid source at the top of the reactor, respectively.

[0115] This implementation follows the same procedures as Examples 1 and 2. In this example, synthesis gas 111A has a flow rate of 1540 NL / h and a feed pressure of 5.5 MPa, which is reduced to 1.6 MPa via a gas distribution pipe; 111B has a flow rate of 380 NL / h and a feed pressure of 2.0 MPa; propylene feed 110 has a flow rate of 1.8 kg / h; the circulating liquid volumetric flow rate is 150 L / h; and the gas circulation rate is 170 L / h. The butyraldehyde yield is 3.06 kg / h, which translates to a propylene-to-butyraldehyde conversion rate of 99.2%. The measured butyraldehyde space-time yield (STY) is 4.25 mol / (l*h), and the product normal-to-isotropic ratio is 37.

[0116] Example 4

[0117] Using the method described in Example 1, the catalyst had a rhodium concentration of 60 ppm, and the ligands were a combination of tris(o-methylphenyl)phosphine L0 and L4, wherein the molar ratio of Rh:L0:L4 was 1:10:4. Experiments were conducted using ethylene as the olefin feedstock.

[0118] In this embodiment, synthesis gas 111A is 2250 NL / h, with a feed pressure of 5.5 MPa, which is reduced to 1.6 MPa through a gas distribution pipe; 111B is 400 NL / h, with a feed pressure of 2.0 MPa; ethylene feed 110 is 1.65 kg / h, the circulating liquid volumetric flow rate is 150 L / h, and the gas circulation rate is 170 L / h. The propionaldehyde yield is 3.40 kg / h, which translates to a 99.3% conversion rate from ethylene to propionaldehyde. The measured propionaldehyde space-time yield (STY) is 5.86 mol / (L*h).

[0119] Example 5

[0120] Using the method described in Example 2, the catalyst had a rhodium concentration of 60 ppm, and the ligands were a combination of tris(o-methylphenyl)phosphine L0 and L5, wherein the molar ratio of Rh:L0:L5 was 1:10:4. Experiments were conducted using ethylene as the olefin feedstock.

[0121] In this embodiment, synthesis gas 111A is 2250 NL / h, with a feed pressure of 5.5 MPa, which is reduced to 1.6 MPa through a gas distribution pipe; 111B is 400 NL / h, with a feed pressure of 2.0 MPa; ethylene feed 110 is 1.65 kg / h, the circulating liquid volumetric flow rate is 150 L / h, and the gas circulation rate is 170 L / h. The propionaldehyde yield is 3.40 kg / h, which translates to a 99.3% conversion rate from ethylene to propionaldehyde. The measured propionaldehyde space-time yield (STY) is 5.86 mol / (L*h).

[0122] Example 6

[0123] Using the method described in Example 2, with a rhodium concentration of 150 ppm as the catalyst and triphenylphosphine as the ligand, experiments were conducted using ethylene as the olefin feedstock.

[0124] In this embodiment, synthesis gas 111A is 2250 NL / h, with a feed pressure of 5.5 MPa, which is reduced to 1.6 MPa through a gas distribution pipe; 111B is 400 NL / h, with a feed pressure of 2.0 MPa; ethylene feed 110 is 1.65 kg / h, the circulating liquid volumetric flow rate is 150 L / h, and the gas circulation rate is 170 L / h. The propionaldehyde yield is 2.80 kg / h, which translates to a conversion rate of 82% from ethylene to propionaldehyde. The measured propionaldehyde space-time yield (STY) is 4.83 mol / (L*h).

[0125] Example 7

[0126] The method of Example 1 is used, but an ethylene-propylene mixed gas is used as the olefin feedstock, wherein the ethylene-propylene mixing ratio is 1:4.

[0127] In this embodiment, synthesis gas 111A has a flow rate of 1950 NL / h and a feed pressure of 5.5 MPa, which is reduced to 1.6 MPa through a gas distribution pipe; 111B has a flow rate of 350 NL / h and a feed pressure of 2.0 MPa; the mixed olefin feed 110 contains 0.75 kg / h of ethylene and 1.0 kg / h of propylene, with a circulating liquid volume flow rate of 150 L / h and a gas circulation flow rate of 170 L / h. The propionaldehyde yield is 1.54 kg / h, which translates to a 99.4% conversion rate from ethylene to propionaldehyde. The measured propionaldehyde space-time yield (STY) is 2.66 mol / (L*h); the butyraldehyde yield is 1.70 kg / h, which translates to a 99.3% conversion rate from propylene to butyraldehyde. The measured butyraldehyde space-time yield (STY) is 2.36 mol / (L*h), and the product normal-to-iso ratio is 30.

[0128] Comparative Example 1

[0129] Use the same method as in Example 1, but close the connection pipe 19 between the injector 16 and the top of the reactor.

[0130] In this embodiment, synthesis gas 111A has a flow rate of 1540 NL / h and a feed pressure of 5.5 MPa, which is reduced to 1.6 MPa through a gas distribution pipe; 111B has a flow rate of 380 NL / h and a feed pressure of 2.0 MPa; propylene feed 110 has a flow rate of 1.8 kg / h, the circulating liquid volume flow rate is 150 L / h, and gas circulation line 19 is closed, with the gas circulation volume displayed as (0 L / h). The butyraldehyde yield is 2.45 kg / h, which translates to a propylene-to-butyraldehyde conversion rate of 79.5%. The measured butyraldehyde space-time yield (STY) is 3.40 mol / (l*h), and the product normal-to-isotropic ratio is 30.

[0131] Comparative Example 2

[0132] Using the same method as Comparative Example 1, the connection pipe 111B between the injector and the gas source was simultaneously shut off. As a result, all the synthesis gas was fed into the gas distributor 11 without depressurization, and a bubbling reaction was carried out in the liquid phase containing the catalyst and reaction mixture.

[0133] In this embodiment, the injector is used only for liquid circulation and propylene feed. All synthesis gas is fed from the bottom of the reactor: 111A has a flow rate of 1920 NL / h, and the pressure at the distributor is 2.0 MPa; 111B has a flow rate of 0 NL / h; propylene feed 110 has a flow rate of 1.8 kg / h, the circulating liquid volumetric flow rate is 150 L / h, and gas circulation line 19 is closed. The gas circulation volume is displayed as (0 L / h). The butyraldehyde yield is 2.35 kg / h, which translates to a propylene-to-butyraldehyde conversion rate of 78%. The measured butyraldehyde space-time yield (STY) is 3.24 mol / (L*h), and the product normal-to-isotropic ratio is 25.

[0134] Comparative Example 3

[0135] Using the method described in Example 1, the catalyst concentration was 60 ppm, and the ligands were a combination of tris(o-methylphenyl)phosphine L0 and L4, wherein the molar ratio of Rh:L0:L4 was 1:10:4. Experiments were conducted using ethylene as the olefin feedstock. The connection pipe 19 between the injector 16 and the top of the reactor was closed, and the connection pipe 111B between the injector and the gas source was shut off.

[0136] In this embodiment, the synthesis gas 111A is 2400 NL / h, the feed pressure is 5.5 MPa, and it is reduced to 1.6 MPa through the gas distribution pipe; the flow rate of 111B is 0 NL / h; the ethylene feed 110 is 1.5 kg / h, the circulating liquid volume flow rate is 150 L / h, the gas circulation line 19 is closed, and the gas circulation volume is displayed as (0 L / h). The propionaldehyde yield is 2.73 kg / h, which translates to a propionaldehyde conversion rate of 88.0% for ethylene. The measured propionaldehyde space-time yield STY = 4.71 mol / (l*h), and the product normal-to-iso ratio is 30.

[0137] Example 8

[0138] use Figure 5 The reaction system shown uses ethylene as the olefin feedstock. The catalyst has a rhodium concentration of 60 ppm, and the ligands are a combination of tris(o-methylphenyl)phosphine L0 and L4, with a molar ratio of Rh:L0:L4 of 1:10:4. The reactor temperature is maintained at 90°C, the reaction pressure at 1.6 MPa, the effective reaction liquid volume of a single reactor is 10 L, the total reactor volume of two reactors in series is 20 L, the reactor height is 900 mm, and a self-priming injector 16 is installed at the top with a nozzle diameter of 2.5 mm, a spray angle of 30°, a spray expansion tube diameter of 20 mm, and a spray tube expansion tube length of 850 mm. The gas intake section of the injector 16 has two gas inlets, connected to a gas source and a fluid source at the top of the reactor, respectively.

[0139] In this embodiment, the synthesis gas flow rate is 5450 NL / h, with 80% allocated to the first reactor at 4360 NL / h, all entering 100A via distributor 11; 110A displays 0 NL / h. The second reactor receives 20% allocated at 1090 NL / h, all entering 100B via distributor 11; 110B displays 0 NL / h. The feed pressure for both reactors is 5.5 MPa, reduced to 1.6 MPa via the gas distribution pipe. The ethylene feed rate to 111 is 3.4 kg / h, the circulating liquid volumetric flow rate is 150 L / h, and the gas circulation rate is 170 L / h. The propionaldehyde yield is 7.0 kg / h, which translates to a 99.5% conversion rate from ethylene to propionaldehyde. The measured propionaldehyde space-time yield (STY) is 6.03 mol / (l*h).

[0140] Example 9

[0141] use Figure 6 The reaction system shown uses ethylene as the olefin feedstock. The catalyst has a rhodium concentration of 60 ppm, and the ligands are a combination of tris(o-methylphenyl)phosphine L0 and L4, with a molar ratio of Rh:L0:L4 of 1:10:4. The reactor temperature is maintained at 90°C, the reaction pressure at 1.6 MPa, the effective reaction liquid volume of reactor 10 is 10 L, the reactor height is 900 mm, and a self-priming injector 16 is installed at the top. The injector has a nozzle diameter of 2.5 mm, a spray angle of 30°, a spray expansion tube diameter of 20 mm, and a spray tube expansion tube length of 850 mm. The gas intake section of injector 16 has only one gas inlet, which is connected to both the gas source and the fluid at the top of the reactor via a Y-shaped pipe.

[0142] In this embodiment, synthesis gas 111A is 2250 NL / h, with a feed pressure of 5.5 MPa, which is reduced to 1.6 MPa through a gas distribution pipe; 111B is 400 NL / h, with a feed pressure of 2.0 MPa; ethylene feed 110 is 1.65 kg / h, the circulating liquid volumetric flow rate is 150 L / h, and the gas circulation rate is 170 L / h. The propionaldehyde yield is 3.22 kg / h, which translates to a 94.5% conversion rate from ethylene to propionaldehyde. The measured propionaldehyde space-time yield (STY) is 5.55 mol / (L*h).

[0143] Example 10

[0144] Using the method described in Example 2, n-butene was selected as the olefin feedstock, wherein the mass ratio of 1-butene to 2-butene was 1:2; the catalyst concentration was 200 ppm; and the ligands were a combination of tris(o-methylphenyl)phosphine L0 and L5, wherein the molar ratio of Rh:L0:L5 was 1:10:4. The reactor temperature was maintained at 95°C, and the reaction pressure was 1.5 MPa.

[0145] In this embodiment, synthesis gas 111A has a flow rate of 1430 NL / h and a feed pressure of 5.5 MPa, which is reduced to 1.6 MPa through a gas distribution pipe; 111B has a flow rate of 350 NL / h and a feed pressure of 2.0 MPa; the mixed butene feed 110 has a flow rate of 2.2 kg / h, the circulating liquid volumetric flow rate is 150 L / h, and the gas circulation rate is 170 L / h. The pentanal yield is 3.26 kg / h, which translates to a conversion rate of 96.5% from mixed butene to pentanal. The measured space-time yield of pentanal is STY = 3.79 mol / (l*h).

[0146] Example 11

[0147] Using the method described in Example 2, 1-pentene was selected as the olefin feedstock; the catalyst had a rhodium concentration of 200 ppm, and the ligands were a combination of tris(o-methylphenyl)phosphine L0 and L5, wherein the molar ratio of Rh:L0:L4 was 1:10:4. The reactor temperature was maintained at 100°C, and the reaction pressure was 1.5 MPa.

[0148] In this embodiment, synthesis gas 111A is 1150 NL / h, with a feed pressure of 5.5 MPa, which is reduced to 1.6 MPa through a gas distribution pipe; 111B is 270 NL / h, with a feed pressure of 2.0 MPa; 1-pentene feed 110 is 2.2 kg / h, the circulating liquid volumetric flow rate is 150 L / h, and the gas circulation rate is 170 L / h. The hexanal yield is 3.01 kg / h, which translates to a pentene-to-hexanal conversion rate of 96.0%. The measured hexanal space-time yield (STY) is 3.00 mol / (L*h).

Claims

1. A hydroformylation synthesis reactor, comprising a bottom-spray self-priming reactor placed at the top of the reactor, the bottom-spray self-priming reactor comprising, in sequence, a nozzle and a fluidly connected intake section, a mixing section and a diffusion section, the nozzle being located within the intake section, the intake section being in communication with a raw material gas source fluid; Its features The intake section is also connected to the fluid above the liquidus line of the reactor via a pipe, and the reactor also includes a gas distributor inside the reactor and connected to the raw material gas source fluid. The reactor is a bubble column reactor. The nozzle of the down-spray self-priming reactor is used to spray a catalyst-containing reaction liquid into the reactor. The reaction liquid entrains a portion of the gaseous raw material from the gas source and the circulating gas from the gas phase of the reactor in the gas intake section, and mixes, reacts and diffuses in the mixing section and the diffusion section. The gas distributor is used to send another portion of the gaseous raw material from the gas source through a pipeline into the reactor, where it reacts with the catalyst-containing solution by bubbling in the reactor liquid.

2. The reaction vessel as described in claim 1, characterized in that... Each reactor includes two parallel down-spray self-priming reactors. Each down-spray self-priming reactor includes, in sequence, a nozzle and a fluid-connected intake section, a mixing section, and a diffusion section. Each nozzle is located within the intake section, and each intake section is connected to the raw material gas source fluid. Furthermore, each intake section is also connected to the fluid above the liquidus line of the reactor via a pipe.

3. The reaction vessel as described in claim 1, characterized in that... The intake section, mixing section, and diffusion section each constitute a Venturi tube.

4. The reaction vessel as described in claim 1, characterized in that... The intake section of the downspout self-priming reactor has two gas inlets, which are respectively connected to the gas source and the fluid above the liquidus line of the reactor.

5. A reaction system for a hydroformylation synthesis reaction, comprising: The reactor includes a bottom-spray self-priming reactor mounted on its top. The reactor sequentially includes a nozzle and a fluidly connected intake section, mixing section, and diffusion section. The nozzle is located within the intake section, which is in fluid communication with the feed gas source. The intake section is also in fluid communication with the portion of the reactor above the liquidus line via a pipe. The reactor also includes a gas distributor inside the reactor and in fluid communication with the feed gas source, a reactor outlet mounted at its lower part for discharging the reaction mixture and catalyst solution, and a distribution plate mounted between the bottom-spray self-priming reactor and the reactor outlet for altering the flow of olefins and syngas. and A circulation pipe is used to recover the reaction mixture from the reactor outlet and then supply it to the nozzle of the downspout self-priming reactor to circulate the reaction mixture and catalyst solution. The reactor is a bubble column reactor. The nozzle of the down-spray self-priming reactor is used to spray a catalyst-containing reaction liquid into the reactor. The reaction liquid entrains a portion of the gaseous raw material from the gas source and the circulating gas from the gas phase of the reactor in the gas intake section, and mixes, reacts and diffuses in the mixing section and the diffusion section. The gas distributor is used to send another portion of the gaseous raw material from the gas source through a pipeline into the reactor, where it reacts with the catalyst-containing solution by bubbling in the reactor liquid.

6. The reaction system as described in claim 5, characterized in that... It comprises two reaction vessels, the gas phase portions of which are fluidly connected by pipes.

7. The reaction system as described in claim 5, characterized in that... Each reactor includes two parallel down-spray self-priming reactors. Each down-spray self-priming reactor includes, in sequence, a nozzle and a fluid-connected intake section, a mixing section, and a diffusion section. Each nozzle is located within the intake section, and each intake section is connected to the raw material gas source fluid. Furthermore, each intake section is also connected to the fluid above the liquidus line of the reactor via a pipe.

8. The reaction system as described in claim 5, characterized in that... The intake section, mixing section, and diffusion section each constitute a Venturi tube.

9. The reaction system as described in claim 5, characterized in that... The intake section of the downspout self-priming reactor has two gas inlets, which are respectively connected to the gas source and the fluid above the liquidus line of the reactor.

10. Use of the hydroformylation synthesis reactor as described in claim 1 in the preparation of aldehydes from olefins.

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